Environmental Forensics, 9:117120, 2008 Copyright C Taylor & Francis Group, LLC ISSN: 15275922 print / 15275930 online

DOI: 10.1080/15275920802115324

Commentary Comments on the Reported Unusual Progression of Petroleum Hydrocarbon Distribution Patterns During Environmental Weathering
Yakov Galperin1 and Isaac R. Kaplan2
Environmental Geochemistry Consulting, Moorpark, CA, USA Department of Earth & Space Sciences and Institute of Geophysics & Planetary Physics, University of California, Los Angeles, CA, USA
2 1

Keywords: hydrocarbon ngerprinting, petroleum degradation, methanogenic biodegradation, alkane degradation

Over the past 5 years, a group of United States Geological Survey (USGS) researchers published a series of articles (Hostettler and Kvenvolden, 2002; Bekins et al., 2005; Hostettler et al., 2007) suggesting a rather unusual progression of petroleum degradation in the subsurface environment under anoxic (predominantly methanogenic) conditions. Based on results of the two eld studies, the researchers concluded that for the >C10 petroleum fraction, degradation under methanogenic conditions depletes the longer chain normal alkanes (n-alkanes), nalkylcyclohexanes and n-alkylbenzenes before the shorter chain homologs. Moreover, Hostettler et al. (2007) stated that nalkyl[-substituted] compounds are apparently attacked at the end of n-alkane chains, resulting in the formation of progressively lower MW homologs. . . (p. 152). USGS researchers warned thatif unrecognizedthe effect of this process on a degraded petroleum product ngerprint could be erroneously attributed to admixture of a lower boiling petroleum product (Hostettler and Kvenvolden, 2002). Whereas preferential methanogenic degradation of heavier n-alkanes was reported for gasoline range (<C10 ) hydrocarbons (Siddique et al., 2006, 2007), we were unable to nd published results supporting similar progression of biodegradation for heavier (>C10 ) homologs, or biogenic formation of lower-molecular-weight n-alkanes by breaking down highermolecular-weight n-alkane homologs. Apart from the previously
Received 14 November 2007; accepted 1 December 2007. Address correspondence to Yakov Galperin, Environmental Geochemistry Consulting, 13543 Bear Valley Road, Moorpark, CA 93021. E-mail: ygalperin@aol.com

referenced USGS publications, other publications that address the issue of weathering by biodegradation support a degradation progression with preferential depletion of lighter members of n-alkane homologues series (Wilkes et al., 1995, 2007; Swannell et al., 1996; Grishchenkov et al., 2000; Widdel and Rabus, 2001; Artz et al., 2002; Townsend et al., 2003; Davidova et al., 2005). Our literature search disclosed that photooxidation is the only environmental degradation process that reportedly generates lower-molecular-weight n-alkanes (Dutta and Harayama, 2000). Considering the current status of scientic knowledge concerning the mechanism of methanogenic transformation of n-alkanes, n-alkylcyclohexanes, and n-alkylbenzenes (Widdel and Rabus, 2001; Gieg and Suita, 2002; Young and Phelps, 2005), the degradation progression proposed by the USGS researchers should be considered a hypothesis until conrmed or invalidated by additional studies. However, they proceeded to offer this untested hypothesis as a decisive argument in a multimillion-dollar environmental litigation (Hostettler et al., 2007). Results of the laboratory incubation experiment published by the USGS group (Hostettler et al., 2007) seem to provide some degree of support to their hypothesis for n-alkanes degradation progression under methanogenic conditions. However, results of an independent laboratory study of methanogenic degradation of alkanes in crude oil added to anaerobic microcosms inoculated with estuarine sediment (Aitken et al., 2007) contradicts the USGS group results and displays a conventional progression that shows no relative enrichment of the lower-molecular-weight n-alkanes (Figure 1). 117

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Figure 1. Gas chromatograms of A) undegraded North Sea crude oil and B) same crude oil after 15 months laboratory degradation under methanogenic conditions (modied from Aitken et al., 2007).

The following discussion concerns two case studies that Hostettler and her colleagues relied on in formulating the hypothesis of the unique pattern of petroleum degradation under methanogenic condition. The rst case represents a long-term diesel fuel spill in Mandan, North Dakota. Based on their investigation, USGS researchers concluded that the observed shift towards the lighter hydrocarbons in the maximum of n-alkanes and n-alkylcyclohexanes distribution patterns was due to the unique methanogenic progression of the fuel degradation as described previously (Hostettler and Kvenvolden, 2002). From the onset of the investigation, Hostettler and Kvenvolden (2002) assumed that the only documented spill component is diesel fuel from the railway yard in the downtown area (p. 295). However, the site has had a prolonged history of multiple releases at different locations (Roberts, 2001), which suggests variability in chemical composition of the diesel fuel released. In addition, a study performed by the independent group of researchers identied a source of a lighter petroleum product, kerosene, located

Figure 2. Distribution pattern of n-alkanes in sample BE-31 (modied from Hostettler et al., 2007). Pr, pristane.

upgradient from the diesel fuel plume (Stout et al., 2006; Stout and Uhler, 2006). This second group then concluded that the observed changes in hydrocarbon ngerprints could be explained by a mixing of diesel and kerosene fuel plumes. The second case is the August 20, 1979, accidental crude oil spill from a ruptured pipeline in the vicinity of Bemidji, Minnesota. Among the main reasons for selecting this site for a long-term study USGS listed the introduction of a source of uniform composition at a known place and time (USGS, 2006). Although USGS researchers claim that this oil release is well documented and characterized, their investigation at the site began in May 1983, nearly 4 years after the accident and after an extensive recovery effort by the pipeline company. Whereas major details of this recovery effort appear to be well documented (Hult, 1984), there is a good possibility that some of the recovery procedures could have caused pronounced changes in the chemical composition of the crude oil released. It is also noteworthy that the rupture of a shallow, high-pressure pipeline has resulted in a large spray zone covering approximately 7500 m2 of land surface. For at least 1 month, the oil released on the ground was exposed to the atmosphere, which undoubtedly caused changes in its chemical composition. The oil originally pooled at a few topographic depressions and, after approximately 70% of the crude oil was recovered by pumping from surface pools, trenching and excavation, or surface burning, the residual oil percolated down to the groundwater, forming a separate-phase hydrocarbon layer on the water table. It is likely that due to the differences in time of the surface exposure and migration pathways, even at the very beginning of the subsurface degradation period, residual crude oil contamination at different locations in the vadose zone and

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Figure 3. Distribution pattern of n-alkanes in fresh Alberta crude oil (modied from Wang et al., 2003).

Figure 4. Distribution pattern of n-alkanes in evaporated (36.8% wt.) Alberta crude oil (modied from Wang et al., 2003).

separate-phase crude oil oating on the water table could have variable degrees of chemical alteration compared with the initial crude oil composition. This heterogeneity of crude oil chemical composition at the initial stages of subsurface degradation has not been accounted for in the USGS researchers interpretation of analytical data. For the Bemidji oil spill case, the observed changes in distribution patterns of major homologs series of hydrocarbons were reportedly compared with the corresponding patterns in a sample of, archived original crude oil (sample BE-31; However, the n-alkane prole of this sample (Figure 2; Hostettler et al., 2007) does not seem to corroborate this claim. A reduced abundance of light-end alkanes in this sample is not typical of unaltered Alberta crude oil that was released at the site. A published n-alkane prole of unaltered Alberta crude oil presented in Figure 3 (Wang et al., 2003) exhibits an unmistakably different distribution with a much higher content of the light-end hydrocarbons. The difference may be due to some kind of environmental alteration of crude oil in reference sample BE-31. The n-alkane prole of sample BE-31 (Figure 2) appears to exhibit similarity with that of a weathered by evaporation (36.8% weight loss) Alberta crude oil shown in Figure 4 (Wang et al., 2003). This observation suggests that reference oil sample BE-31 represents crude oil that has been already altered by a weathering process (e.g., evaporation) and therefore may be invalid as a reference standard for the composition of the released unaltered crude oil.

This brief discussion provides a basis for the alternative interpretation of analytical data obtained at Mandan, North Dakota, and Bemidji, Minnesota, sites. Currently, the proposed progression of petroleum hydrocarbon distribution patterns by USGS researchers can be considered as an interesting hypothesis that requires a careful evaluation. In conclusion, we would like to point out an obvious misrepresentation by USGS group of the previously published studies. According to Hostettler et al. (2007), they introduced this unusual progression of petroleum degradation as opposed to a widely accepted degradation sequence in aerobic environment described by Kaplan et al. (1997) and Wang et al. (1998). However, these latter publications discuss cumulative changes in chemical composition of petroleum products resulting from physical and biochemical weathering in a typical subsurface environment, without referring to specic redox conditions.

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